US3959207A - Latex viscosity depressants - Google Patents
Latex viscosity depressants Download PDFInfo
- Publication number
- US3959207A US3959207A US05/328,212 US32821273A US3959207A US 3959207 A US3959207 A US 3959207A US 32821273 A US32821273 A US 32821273A US 3959207 A US3959207 A US 3959207A
- Authority
- US
- United States
- Prior art keywords
- latex
- viscosity
- polymer latex
- group
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 146
- 239000004816 latex Substances 0.000 title claims abstract description 108
- ASWOQSUJILLKKH-UHFFFAOYSA-N 2,4,6-tris(2-methylpentan-2-yl)phenol Chemical compound CCCC(C)(C)C1=CC(C(C)(C)CCC)=C(O)C(C(C)(C)CCC)=C1 ASWOQSUJILLKKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 39
- 230000000994 depressogenic effect Effects 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 3
- 229920006173 natural rubber latex Polymers 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- 101001128694 Homo sapiens Neuroendocrine convertase 1 Proteins 0.000 claims 1
- 101000601394 Homo sapiens Neuroendocrine convertase 2 Proteins 0.000 claims 1
- 101000828971 Homo sapiens Signal peptidase complex subunit 3 Proteins 0.000 claims 1
- 101000979222 Hydra vulgaris PC3-like endoprotease variant A Proteins 0.000 claims 1
- 101000979221 Hydra vulgaris PC3-like endoprotease variant B Proteins 0.000 claims 1
- 102100032132 Neuroendocrine convertase 1 Human genes 0.000 claims 1
- 102100037732 Neuroendocrine convertase 2 Human genes 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 abstract description 20
- 239000007787 solid Substances 0.000 description 17
- -1 alkyl radicals Chemical class 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920001821 foam rubber Polymers 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- MOQHZGCCXNGUPE-UHFFFAOYSA-N 2,4-bis(2,4-dimethylheptan-2-yl)phenol Chemical compound CCCC(C)CC(C)(C)C1=CC=C(O)C(C(C)(C)CC(C)CCC)=C1 MOQHZGCCXNGUPE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229940096992 potassium oleate Drugs 0.000 description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- VDOJQPKPGQMNDA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VDOJQPKPGQMNDA-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SYSCLFGZWOBWRQ-UHFFFAOYSA-N 2,3-bis(2-methylpentan-2-yl)-4-octadecan-2-ylphenol Chemical compound CCCCCCCCCCCCCCCCC(C)C1=CC=C(O)C(C(C)(C)CCC)=C1C(C)(C)CCC SYSCLFGZWOBWRQ-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- NIYLXZIMUDICSA-UHFFFAOYSA-N 2,4,6-tri(nonyl)phenol Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=C(O)C(CCCCCCCCC)=C1 NIYLXZIMUDICSA-UHFFFAOYSA-N 0.000 description 1
- VFLCOUPHFUJJTO-UHFFFAOYSA-N 2,4,6-tripentylphenol Chemical compound CCCCCC1=CC(CCCCC)=C(O)C(CCCCC)=C1 VFLCOUPHFUJJTO-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- RQENCFYPRXZBDL-UHFFFAOYSA-N 2,4,6-tris(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC(C(C)(C)CC(C)(C)C)=C(O)C(C(C)(C)CC(C)(C)C)=C1 RQENCFYPRXZBDL-UHFFFAOYSA-N 0.000 description 1
- ALHSGQYMQLAUDI-UHFFFAOYSA-N 2,4,6-tris(decan-2-yl)phenol Chemical compound CCCCCCCCC(C)C1=CC(C(C)CCCCCCCC)=C(O)C(C(C)CCCCCCCC)=C1 ALHSGQYMQLAUDI-UHFFFAOYSA-N 0.000 description 1
- WDCBBGBCYDWLFE-UHFFFAOYSA-N 2,4-bis(2,4-dimethylheptan-2-yl)-6-(2-methylbutan-2-yl)phenol Chemical compound CCCC(C)CC(C)(C)C1=CC(C(C)(C)CC)=C(O)C(C(C)(C)CC(C)CCC)=C1 WDCBBGBCYDWLFE-UHFFFAOYSA-N 0.000 description 1
- VIWRYMZDLJWIAJ-UHFFFAOYSA-N 2,4-bis(2,4-dimethylheptan-2-yl)-6-methylphenol Chemical compound CCCC(C)CC(C)(C)C1=CC(C)=C(O)C(C(C)(C)CC(C)CCC)=C1 VIWRYMZDLJWIAJ-UHFFFAOYSA-N 0.000 description 1
- IOHOXICUFCTPHY-UHFFFAOYSA-N 2,4-di(decan-2-yl)phenol Chemical compound CCCCCCCCC(C)C1=CC=C(O)C(C(C)CCCCCCCC)=C1 IOHOXICUFCTPHY-UHFFFAOYSA-N 0.000 description 1
- IUXGFMNAHJNCMH-UHFFFAOYSA-N 2,4-di(dodecan-2-yl)-6-methylphenol Chemical compound CCCCCCCCCCC(C)C1=CC(C)=C(O)C(C(C)CCCCCCCCCC)=C1 IUXGFMNAHJNCMH-UHFFFAOYSA-N 0.000 description 1
- CZGAOHSMVSIJJZ-UHFFFAOYSA-N 2,4-dimethyl-1-heptene Chemical compound CCCC(C)CC(C)=C CZGAOHSMVSIJJZ-UHFFFAOYSA-N 0.000 description 1
- MJGNFIKMQVQKRC-UHFFFAOYSA-N 2,6-bis(2-methylpentan-2-yl)-6-octan-2-ylcyclohexa-2,4-dien-1-ol Chemical compound CCCCCCC(C)C1(C(C)(C)CCC)C=CC=C(C(C)(C)CCC)C1O MJGNFIKMQVQKRC-UHFFFAOYSA-N 0.000 description 1
- WYUANIUCNJJLIY-UHFFFAOYSA-N 2,6-ditert-butyl-4-(2-methylheptan-2-yl)phenol Chemical compound CCCCCC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WYUANIUCNJJLIY-UHFFFAOYSA-N 0.000 description 1
- YZUYDHQEUJQTOI-UHFFFAOYSA-N 2,6-ditert-butyl-4-hexylphenol Chemical compound CCCCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 YZUYDHQEUJQTOI-UHFFFAOYSA-N 0.000 description 1
- PUYMCMOGLGTIQA-UHFFFAOYSA-N 2,6-ditert-butyl-4-octadecan-2-ylphenol Chemical compound CCCCCCCCCCCCCCCCC(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PUYMCMOGLGTIQA-UHFFFAOYSA-N 0.000 description 1
- HZVGSTCRYFRXGT-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)-4,6-bis(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=C1O HZVGSTCRYFRXGT-UHFFFAOYSA-N 0.000 description 1
- CQOGUKZMGWWLHX-UHFFFAOYSA-N 2-(2-methylpentan-2-yl)-4,6-bis(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CCCC(C)(C)C1=CC(C(C)(C)CC(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=C1O CQOGUKZMGWWLHX-UHFFFAOYSA-N 0.000 description 1
- INIVZTRFGGZKDZ-UHFFFAOYSA-N 2-butyl-4,6-dipentylphenol Chemical compound CCCCCC1=CC(CCCC)=C(O)C(CCCCC)=C1 INIVZTRFGGZKDZ-UHFFFAOYSA-N 0.000 description 1
- KBWGOJDXDZZXIC-UHFFFAOYSA-N 2-butyl-6-hexyl-4-octylphenol Chemical compound CCCCCCCCC1=CC(CCCC)=C(O)C(CCCCCC)=C1 KBWGOJDXDZZXIC-UHFFFAOYSA-N 0.000 description 1
- VGWDRNAPMSQMQE-UHFFFAOYSA-N 2-ethyl-4,6-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC(CC)=C(O)C(CCCCCCCCC)=C1 VGWDRNAPMSQMQE-UHFFFAOYSA-N 0.000 description 1
- LLHPHCGRKSZQRK-UHFFFAOYSA-N 2-ethyl-4,6-di(tetradecan-2-yl)phenol Chemical compound CCCCCCCCCCCCC(C)C1=CC(CC)=C(O)C(C(C)CCCCCCCCCCCC)=C1 LLHPHCGRKSZQRK-UHFFFAOYSA-N 0.000 description 1
- LIUDZCIKFBEXOG-UHFFFAOYSA-N 2-heptyl-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CCCCCCCC1=CC(C(C)(C)CC(C)(C)C)=CC=C1O LIUDZCIKFBEXOG-UHFFFAOYSA-N 0.000 description 1
- YSHHJJAMISGFCW-UHFFFAOYSA-N 2-heptyl-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(CCCCCCC)=C1 YSHHJJAMISGFCW-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- QEMHBAGGYKJNSS-UHFFFAOYSA-N 2-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O QEMHBAGGYKJNSS-UHFFFAOYSA-N 0.000 description 1
- XOOXOSPOXSLLPV-UHFFFAOYSA-N 2-methyl-4,6-bis(2,3,3,4-tetramethylpentan-2-yl)phenol Chemical compound CC(C)C(C)(C)C(C)(C)C1=CC(C)=C(O)C(C(C)(C)C(C)(C)C(C)C)=C1 XOOXOSPOXSLLPV-UHFFFAOYSA-N 0.000 description 1
- MEVKWAXDAZDZJX-UHFFFAOYSA-N 2-methyl-4,6-di(tetradecan-2-yl)phenol Chemical compound CCCCCCCCCCCCC(C)C1=CC(C)=C(O)C(C(C)CCCCCCCCCCCC)=C1 MEVKWAXDAZDZJX-UHFFFAOYSA-N 0.000 description 1
- LGHAHHNCUSXESC-UHFFFAOYSA-N 2-methyl-4,6-dioctylphenol Chemical compound CCCCCCCCC1=CC(C)=C(O)C(CCCCCCCC)=C1 LGHAHHNCUSXESC-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- QZDIGKQKIYTXIS-UHFFFAOYSA-N 2-tert-butyl-4,6-bis(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)CC(C)(C)C)=C1 QZDIGKQKIYTXIS-UHFFFAOYSA-N 0.000 description 1
- HMUJTYDNRDANBC-UHFFFAOYSA-N 2-tert-butyl-4-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=C(O)C(C(C)(C)C)=C1 HMUJTYDNRDANBC-UHFFFAOYSA-N 0.000 description 1
- FHNPMBMKZNSSDX-UHFFFAOYSA-N 4-(2,4-dimethylheptan-2-yl)-2,6-bis(2-methylpentan-2-yl)phenol Chemical compound CCCC(C)CC(C)(C)C1=CC(C(C)(C)CCC)=C(O)C(C(C)(C)CCC)=C1 FHNPMBMKZNSSDX-UHFFFAOYSA-N 0.000 description 1
- CMPVIPIWBKEEMQ-UHFFFAOYSA-N 4-(2,4-dimethylheptan-2-yl)-2-(2-methylpentan-2-yl)phenol Chemical compound CCCC(C)CC(C)(C)C1=CC=C(O)C(C(C)(C)CCC)=C1 CMPVIPIWBKEEMQ-UHFFFAOYSA-N 0.000 description 1
- COFZPZCXSQTTKW-UHFFFAOYSA-N 4-butyl-2,4-bis(2-methylbutan-2-yl)cyclohexa-1,5-dien-1-ol Chemical compound CCCCC1(C(C)(C)CC)CC(C(C)(C)CC)=C(O)C=C1 COFZPZCXSQTTKW-UHFFFAOYSA-N 0.000 description 1
- OSLIPRIGMWBOGA-UHFFFAOYSA-N 4-dodecyl-2,6-dimethylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=C(O)C(C)=C1 OSLIPRIGMWBOGA-UHFFFAOYSA-N 0.000 description 1
- BFKNLNWBJUVITE-UHFFFAOYSA-N 4-ethyl-2,6-di(tetradecan-2-yl)phenol Chemical compound CCCCCCCCCCCCC(C)C1=CC(CC)=CC(C(C)CCCCCCCCCCCC)=C1O BFKNLNWBJUVITE-UHFFFAOYSA-N 0.000 description 1
- JMIZYEPCMQULCR-UHFFFAOYSA-N 4-tetradecylphenol;2,4,6-tris(2-methylpentan-2-yl)phenol Chemical compound CCCCCCCCCCCCCCC1=CC=C(O)C=C1.CCCC(C)(C)C1=CC(C(C)(C)CCC)=C(O)C(C(C)(C)CCC)=C1 JMIZYEPCMQULCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000000899 Gutta-Percha Substances 0.000 description 1
- 229910003556 H2 SO4 Inorganic materials 0.000 description 1
- 101001022148 Homo sapiens Furin Proteins 0.000 description 1
- 101000701936 Homo sapiens Signal peptidase complex subunit 1 Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000000342 Palaquium gutta Species 0.000 description 1
- 229920013620 Pliolite Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 102100030313 Signal peptidase complex subunit 1 Human genes 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 238000005703 Whiting synthesis reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 244000001591 balata Species 0.000 description 1
- 235000016302 balata Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920000588 gutta-percha Polymers 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011346 highly viscous material Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940045681 other alkylating agent in atc Drugs 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/925—Natural rubber compositions having nonreactive materials, i.e. NRM, other than: carbon, silicon dioxide, glass titanium dioxide, water, hydrocarbon or halohydrocarbon
- Y10S524/926—Natural rubber compositions having nonreactive materials, i.e. NRM, other than: carbon, silicon dioxide, glass titanium dioxide, water, hydrocarbon or halohydrocarbon with water as NRM, exemplified
Definitions
- This invention relates to the use of certain phenolic antioxidants as depressants of latex viscosity.
- the viscosity of a latex is very dependent upon the concentration of the polymer which it contains. At low concentrations the effect is slight, but it becomes increasingly pronounced as the concentration rises. In general, the viscosity begins to rise exponentially when the volume fraction of the polymer in the latex reaches a value of from about 0.3 to about 0.5. A more dramatic rise normally begins to occur in the range from about 0.4 to about .6.
- Particle size and particle size distribution for a given solids content also affects viscosity. At a given solids content large particle size latices are more fluid than are corresponding latices of smaller particle size.
- Latices also become more viscous as the temperature is increased.
- Latices to be used for foam production are often loaded with inorganic or organic fillers. These fillers include feldspar; clays such as Kaolinite clays; mica; talc; lithopone; aluminum trihydrate and calcium carbonates including the various whitings, chalks and limestones.
- Aluminum trihydrate although an expensive material and not commonly used as a filler, is an important additive where flame proofing is desirable. If the latex is highly viscous, it is difficult to load the latex with these fillers or any other compounding ingredients. That is, mixing rates are reduced because of high latex viscosities.
- compounding ingredients such as fillers can result in higher viscosities.
- the fillers are normally added in amounts from about 10 parts to about 150 parts by weight per 100 parts by weight of polymer in the latex, more normally from about 20 parts to about 120 parts. In certain latex applications, for example in treating paper, higher loadings are used, for example up to 600 parts by weight and higher.
- a light density foam e.g., where the air to latex ratio is approximately 8 to 9 volumes of air to 1 volume of latex
- a high froth viscosity can result in an unmanageable situation at the bank.
- a high froth viscosity can also result in pouring and molding problems.
- Latex spreading compounds require carefully controlled viscosity levels. As well as determining the ease of the handling the compound, viscosity has an important influence upon the extent that the latex will penetrate the fabric. Some degree of penetration is essential but complete penetration to the far side of the fabric is generlly undesirable. Therefore, optimum viscosities must be used. Not only is the bulk viscosity of a spreading compound important, but the nature of the relationship between flow rate and shear is also important.
- viscosity can be an important factor, A centrifuge pump can move highly viscous materials.
- an apparatus such as a blow case, where the latex is drawn in by a vacuum, the pressure raised, and the latex blown out, requires lower viscosity latices.
- the viscosity be less than 2500 centipoises and preferably under 500 centipoises.
- a representative compounded viscosity range used in spreading foam backings for carpeting is 2500 to 2800 centipoises, although viscosities as high as 5000 to 7000 centipoises can be used. It is not unusual for thickeners to be added to latices for this purpose.
- latices are compounded with up to 600 parts of filler and higher.
- a representative maximum viscosity value for the loaded composition is 3000 centipoises. Therefore the latex, before compounding, must possess a low viscosity, a representative range being 200 to 300 centipoises. If the viscosity of the compounded latex is too high, nonuniform distribution on the paper surface can result.
- An object of the present invention is to provide a method of lowering the viscosity of a high viscosity latex without adversely affecting, and in fact in many instances enhancing the other properties of the latex and the polymer contained therein.
- Another object of the present invention is to provide a viscosity suppressant which is also an antioxidant.
- R, R 1 and R 2 are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 24 carbon atoms and wherein the sum of the carbon atoms in R, R 1 and R 2 is from 14 to 32 carbon atoms, preferably 16 to 24 carbon atoms.
- R and R 1 are in positions ortho to the hydroxyl group and contain from 4 to 8 carbon atoms which are attached to the phenolic ring by a tertiary carbon atom.
- Illustrative of such radicals are tert. butyl; 1,1-dimethylpropyl; 1,1-dimethylbutyl; and 1,1,3,3-tetramethylbutyl.
- R 2 is in a position para to the hydroxyl group and contains 6 to 24 carbon atoms preferably 6 to 12 carbon atoms illustrated by the following radicals: hexyl; 1,1-dimethylbutyl; 1-propylbutyl; 1,1,3,3-tetramethylbutyl; 1,1,3-trimethylhexyl; 1,1,3,3,5,5-hexamethylhexyl; dodecyl and 1-methylnonyl.
- All of the phenolic compounds of the present invention offer the polymer latex at least some small degree of protection against oxidative degradation. However, the preferred phenolic compounds above offer a relatively superior degree of antioxidant protection.
- antioxidants of the phenolic compounds described herein among the better viscosity depressants of these compounds are those according to structural formula I where R 2 is an alkyl radical containing 18 to 24 carbon atoms, and is in a position ortho or para, and preferably para, to the hydroxy group.
- R 1 and R 2 are alkyl radicals containing at least 9 carbon atoms each and preferably are in the para and ortho positions.
- the phenolic antioxidants of the present invention are synthesized by well known methods of alkylation of phenol and monosubstituted phenols consisting of o, m and p isomers.
- the preferred process is to treat the phenol or monsubstituted phenol with the appropriate olefins in the presence of a Friedel Craft type catalyst at a temperature of between 0°C. and 150°C.
- Preferred catalysts are H 2 SO 4 , the sulfonic acids and acid activated clays. Exact conditions such as catalyst quantity, temperature, molar ratios of olefin to phenol will depend upon the phenol and olefin being used, but are well known in the art.
- olefins In case of dissimilar groups, such as tert.octyl and tert.butyl, mixtures of olefins may be used, but here it is preferred to react with the least active olefin first.
- alkylating agents such as alcohols and alkyl halides may be used; however, these agents are not preferred.
- Aluminum phenates may also be used as alkylation catalysts.
- the present invention provides a way to reduce latex viscosities, compounded and uncompounded, without causing processing difficulties or adversely affecting the properties of the latex of the products treated with said latex or products fabricated therefrom.
- the viscosity depressants can be added to latices prior to foam formation, thereby decreasing the froth viscosity. This results in easier pouring of the foamed latex and/or improved spreading characteristics when forming carpet backing.
- the depressants can also be added to latices to improve pumping efficiency. Addition to latices to be compounded will permit the addition of higher amounts of inorganic fillers, e.g., where the latex is to be used to coat paper or to form a foamed product.
- the depressants also facilitate easier mixing of the fillers into the latices.
- the depressants can be used to reduce the viscosity of a compounded latex which otherwise would be so viscous that it would result in a non-uniform coating.
- the depressants can also be incorporated into latices whcih are to be used at lower temperatures.
- a fabric is being coated with a latex, and then being dried, it may be necessary due to the high viscosity of the latex, that the fabric be coated slowly to permit sufficient penetration of the latex into the fabric before the drying step.
- the addition of the viscosity supressant to the latex will result in a faster penetration rate and therefore permit a faster coating rate.
- the latices used often possess a high viscosity. This is normally due to the need for high solids latex, for example, 60 percent solids and above and sometimes because of compounding the latex with high amounts, i.e., 50 to 100 parts by weight and above, of fillers.
- the high solids requirement is based on the fact that as low a water level as possible is desirable from a shrinkage and drying standpoint.
- Various problems can result because of the high viscosity. Included in these problems are low pumping rates, low spreading rates, and poor foaming rates.
- the viscosity depressants of the present invention by addition to the latex, can result in reasonable viscosities without sacrificing the high solids contents and high levels of loading. On the other hand, where a highly loaded, high solids latex possesses a reasonable viscosity, but it is desirable to increase solids and/or the loading level without increasing viscosity, the present depressants can be added to the latex.
- the high viscosity latices which benefit by the practice of the present invention are those latices both compounded and uncompounded which have a viscosity of at least 500 centipoises. Viscosity as referred to herein is conveniently measured according to ASTM D 1417-7 (1970 Annual Book of ASTM Standards, Vol. 28), the viscosity normally being measured with a Brookfield Viscometer.
- the depressants are particularly beneficial in latices having even higher viscosities such as those having a viscosity in the absence of these viscosity depressants of at least two or three thousand.
- the depressants are most beneficial in latices having a viscosity of at least 4000 centipoises.
- the polymer latices that can benefit by the practice of the present invention include latices of substituted and unsubstituted, saturated and unsaturated, natural and synthetic polymers.
- the synthetic polymers are prepared by any of the well known free radical emulsion polymerizaton techniques.
- the oxidizable natural polymers include natural rubber in its various forms, e.g., pale crepe and smoked sheet, and balata and gutta percha.
- the oxidizable synthetic polymers, including rubbery synthetic polymers are prepared from a single monomer (homopolymer) or a mixture of two or more copolymerizable monomers (copolymers) wherein the monomers are combined in a random distribution or block form.
- the monomers may be substituted or unsubstituted and may possess one or more double bonds, for example, diene monomers such as conjugated dienes, and polymerizable monoolefins, especially vinyl and vinylidene monomers.
- diene monomers such as conjugated dienes
- polymerizable monoolefins especially vinyl and vinylidene monomers.
- conjugated dienes are 1,3-butadiene, isoprene, chloroprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl 1,3-butadiene and piperylene.
- vinyl monomers are styrene, acrylonitrile, acrylic acid, ethylacrylate, butylacrylate, methyl vinyl ether, vinyl acetate and vinyl pyridine.
- vinylidene monomers are ⁇ -methylstyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and vinylidene chloride.
- Representative examples of the synthetic polymer latices used in the practice of this invention are latices of homopolymers of a conjugated 1,3-diene such as isoprene and butadiene, and copolymers of a conjugated 1,3-diene such as isoprene and butadiene with up to 50 percent by weight of at least one copolymerizable monomer, especially vinyl and vinylidene monomers, such as styrene, acrylonitrile or vinylidene chloride.
- the depressants are particularly beneficial in latices used in the manufacture of foam rubber both natural and synthetic. They are also quite beneficial in latices used to coat and sometimes impregnate paper products.
- the latices used in all of these applications are well known.
- the operations involved in preparing foamed products and in coating and impregnating paper are also quite well known in the art.
- Some of the latices used in forming foam rubber products are described in U.S. Pat. Nos. 3,523,996; 3,496,055; 3,493,523 and 2,649,391.
- Latices for coating paper are represented by those described in U.S. Pat. Nos. 3,047,427 and 3,399,080.
- the latices used in making foam rubber are normally either natural rubber latices or a synthetic rubber latex, at least 40 to 50 percent of the bound monomer units being the segmeric form of a conjugated 1,3-diene such as 1,3-butadiene.
- Typical latices used in coating paper include butadiene-styrene latices and polyacrylate latices.
- the viscosity depressants are added to the latex in liquid form, normally in the form of an emulsion. If the depressant is a solid, it is dissolved in an appropriate organic solvent such as toluene before being emulsified. Conventional emulsifiers, cationic, anionic or non-ionic are used. The solvents used to dissolve the solid depressant should have limited compatibility with the polymer in the latex to which the depressant is added.
- the compounds of the present invention offer at least a small degree of antioxidant effectiveness. Therefore, every one of the depressants of the present invention serves a dual purpose. Not only do they reduce the viscosity of the latex to which they are added, but in addition they protect the polymer at least to some degree against oxidative degradation. They also are relatively nondiscoloring. As a result of their dual functionality, the better antioxidants of the phenolic compounds described herein afford an economic and step saving advantage in that often one need not incorporate two additives, i.e., both a viscosity depressant and an antioxidant, but only one additive which serves both functions.
- the amount of phenolic compound to be added to the latex will depend naturally upon the particular depressant which is added, the viscosity of the latex to which it is added and the desired viscosity. Levels of from 0.10 part to 5.0 parts by weight of depressant per 100 parts by weight of polymer in the polymer latex and higher can be used. Most of the viscosity depressant effect, however, can be obtained normally by using as little as 1.0 to 3.0 parts. A preferred range is 0.25 to 3.0 parts, most preferably from 0.50 to 3.0 parts.
- the viscosity depressant effect of the subject compounds is not normally permanent. Although the viscosity drops quickly as the depressant is added, it tends to rise and return toward the original viscosity with time. It is not completely clear what factors affect this time period. However, it is believed that the duration of depressant activity may be associated with the emulsifier used to emulsify the depressant. It is theorized that possibly when the emulsifier used to emulsify the depressant is similar to the emulsifier used to prepare the polymer latex, the duration of viscosity activity is shortened. Therefore, when it is desirable to reduce viscosity for a particular operation, preferably the depressant is added shortly before the operation.
- the phenolic compound, 2,4,6-tris-(1,1-dimethylbutyl) phenol is prepared in the following manner. Ninety-four grams of phenol and 20 grams of toluene sulfonic acid are heated together at a temperature of 120° C. and 90 grams of 2-methyl-1-pentene are added over a 30 minute period. The mixture is cooled to 30° C. and the remaining 180 grams of 2-methyl-1-pentene are added dropwise over a 2 hour period. The reaction mixture is stirred 30 minutes longer and then neutralized with 20 grams of sodium carbonate in an aqueous solution. After decanting the aqueous layer, the product is stripped to a bottom temperture of 150° C. under vacuum.
- 2,4-bis(1,1,3-trimethylhexyl) phenol is prepared in the following manner. Ninety-four grams of phenol and 20 grams of toluene sulfonic acid are heated together to 85° C. 2,4-dimethyl-1-heptene is added in the amount of 304 grams dropwise over a 3 hour period. The mixture is stirred 2 hours and neutralized with 20 grams of sodium carbonate in aqueous solution. After decanting 5 grams of dry sodium carbonate are added and the product is distilled. The fraction boiling at a column temperature of from 165° C. to 170° C. at 1.1 millimeters of mercury is collected.
- Pliolite* 5362 an SBR latex which can be used for foam rubber applications and having a solids content of approximately 68 percent, was compounded with a feldspar-type filler (125 parts by weight per 100 parts by weight of latex solids).
- Various phenolic compounds were emulsified using potassium oleate and added to the loaded latex. They were all added in the amount of 2.50 parts by weight of the phenolic compound per 100 parts by weight of the latex solids.
- the average viscosity of the latex containg the feldspar-type filler before the addition of the phenolic compounds was 13,470 centipoises using a Model HAT Brookfield Viscometer and a number 2 spindle at 5 revolutions per minute. The viscosity of the latex was measured shortly after the addition of the phenolic compounds.
- a 20 percent aqueous solution of potassium oleate was added to the latex in an amount sufficient to provide 4 parts by weight of potassium oleate per 100 parts by weight of latex solids.
- the oleate aids in stabilizing the latex during the filler addition.
- the feldspar filler was then added in dry form under agitation to the latex. Viscosity measurements were made on the loaded latex, small amounts of water being added if necessary to facilitate easier measurement of the viscosity. Fifty percent aqueous emulsions of the phenolic compounds, with sodium oleate as the emulsifier, were added to the latex under agitation. Viscosity measurements were made shortly thereafter.
- Example 4 involves the use of a trihexylated phenol.
- Example 5 involves a compound which is a mixture of butylated and octylated phenols, one of the main constituents being a phenolic compound containing a butyl group in an ortho position and octyl groups in the ortho and para positions.
- Example 6 involves the use of a phenolic compound having a single large alkyl substituent.
- the Depressant Index was calculated by dividing the viscosity of the loaded latex after the addition of the viscosity depressant by the viscosity of the loaded latex prior to the addition of the viscosity depressant.
- the phenolic compound of Example 6 was butylated and used as a depressant. It's Depressant Index was 0.30.
- viscosity depressants can also be used in combination with other antioxidants such as those described in U.S. Pat. No. 3,305,522.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The viscosity of a high viscosity latex, compounded or uncompounded, is lowered by the addition of certain phenolic compounds such as 2,4,6-tris-(1,1-dimethylbutyl)-phenol.
Description
This is a continuation of application Ser. No. 107,487 filed Jan. 18, 1971, and now abandoned.
This invention relates to the use of certain phenolic antioxidants as depressants of latex viscosity.
Various types of polymer latices are known in the art. They are used for a variety of purposes. Frequently it is necessary to increase the viscosities of the latices in order to enhance their performance in a particular application. This is often accomplished by the addition of compounds known as thickeners. Although much effort has been expended in the area of increasing latex viscosity and in the use of thickeners, relatively little attention has been given to the problem of latex viscosities which are too high for a particular use. Various factors contribute to higher viscosities. Among these are high solids contents, particle size distribution and the presence of large amounts of compounding ingredients such as fillers.
The viscosity of a latex is very dependent upon the concentration of the polymer which it contains. At low concentrations the effect is slight, but it becomes increasingly pronounced as the concentration rises. In general, the viscosity begins to rise exponentially when the volume fraction of the polymer in the latex reaches a value of from about 0.3 to about 0.5. A more dramatic rise normally begins to occur in the range from about 0.4 to about .6.
Particle size and particle size distribution for a given solids content also affects viscosity. At a given solids content large particle size latices are more fluid than are corresponding latices of smaller particle size.
Latices also become more viscous as the temperature is increased. Latices to be used for foam production are often loaded with inorganic or organic fillers. These fillers include feldspar; clays such as Kaolinite clays; mica; talc; lithopone; aluminum trihydrate and calcium carbonates including the various whitings, chalks and limestones. Aluminum trihydrate, although an expensive material and not commonly used as a filler, is an important additive where flame proofing is desirable. If the latex is highly viscous, it is difficult to load the latex with these fillers or any other compounding ingredients. That is, mixing rates are reduced because of high latex viscosities.
The addition of compounding ingredients such as fillers can result in higher viscosities. The fillers are normally added in amounts from about 10 parts to about 150 parts by weight per 100 parts by weight of polymer in the latex, more normally from about 20 parts to about 120 parts. In certain latex applications, for example in treating paper, higher loadings are used, for example up to 600 parts by weight and higher.
If the viscosity of the latex is too high, various problems can arise, whether the latex is compounded or uncompounded.
In the preparation of a light density foam, e.g., where the air to latex ratio is approximately 8 to 9 volumes of air to 1 volume of latex, it may be desirable to lower the viscosity of the latex since the higher the air to latex ratio and the higher the original latex viscosity, the greater is the froth viscosity. When such a light density foam is being used in a bank to spread coat a fabric, a high froth viscosity can result in an unmanageable situation at the bank. A high froth viscosity can also result in pouring and molding problems.
High viscosity latices, compounded or uncompounded, can also result in pumping and metering difficulties.
Latex spreading compounds require carefully controlled viscosity levels. As well as determining the ease of the handling the compound, viscosity has an important influence upon the extent that the latex will penetrate the fabric. Some degree of penetration is essential but complete penetration to the far side of the fabric is generlly undesirable. Therefore, optimum viscosities must be used. Not only is the bulk viscosity of a spreading compound important, but the nature of the relationship between flow rate and shear is also important.
Depending upon the type of pump or other type of apparatus used to move a latex, viscosity can be an important factor, A centrifuge pump can move highly viscous materials. However, an apparatus such as a blow case, where the latex is drawn in by a vacuum, the pressure raised, and the latex blown out, requires lower viscosity latices. For such an apparatus, it is preferable that the viscosity be less than 2500 centipoises and preferably under 500 centipoises.
A representative compounded viscosity range used in spreading foam backings for carpeting is 2500 to 2800 centipoises, although viscosities as high as 5000 to 7000 centipoises can be used. It is not unusual for thickeners to be added to latices for this purpose.
In coating paper, latices are compounded with up to 600 parts of filler and higher. A representative maximum viscosity value for the loaded composition is 3000 centipoises. Therefore the latex, before compounding, must possess a low viscosity, a representative range being 200 to 300 centipoises. If the viscosity of the compounded latex is too high, nonuniform distribution on the paper surface can result.
There are various ways of lowering the viscosity of latices including the addition of water to the latex. However, the addition of water results in reduced drying rates. It also results in shrinking problems where a foam is to be prepared from the latex. Another method of lowering the viscosity of a high solids latex, containing latex particles possessing a small average particle size, is to add a high solid latex with a high average particle size. There is a need for further ways of depressing viscosity. Preferably it should be a simple technique which has no adverse effect on the properties of the latex itself or the products treated with or fabricated from the latex, nor should it result in processing difficulties. Most Preferably it should also perform other functions such as protecting the latex against oxidation.
An object of the present invention is to provide a method of lowering the viscosity of a high viscosity latex without adversely affecting, and in fact in many instances enhancing the other properties of the latex and the polymer contained therein. Another object of the present invention is to provide a viscosity suppressant which is also an antioxidant. Other objects of the present invention will become apparent as the text herein proceeds.
The objects of the present invention are accomplished by incorporating into a high viscosity latex a phenolic antioxidant having the following structural formula: ##SPC1##
wherein R, R1 and R2 are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 24 carbon atoms and wherein the sum of the carbon atoms in R, R1 and R2 is from 14 to 32 carbon atoms, preferably 16 to 24 carbon atoms.
Preferably R and R1 are in positions ortho to the hydroxyl group and contain from 4 to 8 carbon atoms which are attached to the phenolic ring by a tertiary carbon atom. Illustrative of such radicals are tert. butyl; 1,1-dimethylpropyl; 1,1-dimethylbutyl; and 1,1,3,3-tetramethylbutyl. Preferably R2 is in a position para to the hydroxyl group and contains 6 to 24 carbon atoms preferably 6 to 12 carbon atoms illustrated by the following radicals: hexyl; 1,1-dimethylbutyl; 1-propylbutyl; 1,1,3,3-tetramethylbutyl; 1,1,3-trimethylhexyl; 1,1,3,3,5,5-hexamethylhexyl; dodecyl and 1-methylnonyl.
All of the phenolic compounds of the present invention offer the polymer latex at least some small degree of protection against oxidative degradation. However, the preferred phenolic compounds above offer a relatively superior degree of antioxidant protection.
Although not the most outstanding antioxidants of the phenolic compounds described herein, among the better viscosity depressants of these compounds are those according to structural formula I where R2 is an alkyl radical containing 18 to 24 carbon atoms, and is in a position ortho or para, and preferably para, to the hydroxy group.
Also among the more active depressants of the phenolic compounds according to structural formula I are those where R1 and R2 are alkyl radicals containing at least 9 carbon atoms each and preferably are in the para and ortho positions.
The following compounds are illustrative of the phenolic viscosity depressants used within the practice of the present invention.
2,4-dipentyl-6-butylphenol
2,6-di-tert-butyl-4-tert, hexylphenol
2,4,6-tripentylphenol
2,4,6-tris(1,1-dimethylbutyl) phenol 4-tetradecylphenol
2,4-bis(1,1,3,3-tetramethylbutyl)-6-( 1,1-dimethylethyl)phenol
2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol
2-octadecylphenol
2,4,6-tris(1,1,3,3-tetramethylbutyl) phenol
2,4-dioctyl-6-methylphenol
2-eicosylphenol
2,6-dimethyl-4-dodecylphenol
2,4-bis(1,1,2,2,3-pentamethylbutyl)-6-methylphenol
2,4-dinonyl-6-ethylphenol
2,6-di-tert.butyl-4-heptylphenol
2,4-bis(1-methylnonyl) phenol
2,4,6-tris(1-methylnonyl) phenol
2,4-bis(1,1-dimethylpropyl)-4-butylphenol
2,6-bis(1,1-dimethylethyl)-4-hexylphenol
2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol
2,6-bis(1,1-dimethylethyl)-4-(1,1-dimethylhexyl) phenol
2,6-bis(1,1-dimethylethyl-4-eicosylphenol
2,6-bis(1,1-dimethylethyl)-4 -(1-methylheptadecyl) phenol
2,6-bis)1,1-dimethylethyl)-4-(1-methylundecyl) phenol
2-butyl-4-octyl-6-hexyl phenol
2,4-bis(1-methyltridecyl)-6-ethylphenol
2,6-bis(1-methyltridecyl)-4-ethylphenol
2-heptyl-4-octylphenol
2-heptyl-4-(1,1,3,3-tetramethylbutyl) phenol
2-(1,1-dimethylbutyl)-4-(1,1,3-trimethylhexyl) phenol
2,6-di tert.butyl-4-(1,1,3-trimethylhexyl) phenol
2,4-bis(1,1,3-trimethylhexyl) phenol
2,4-bis(1,1,3-trimethylhexyl)-6-methylphenol
2-tert.butyl-4-(1,1,3-trimethylhexyl)-6-methylphenol
2-tert.butyl-4-(1,1,3-trimethylhexyl)-6-ethylphenol
2-tert.butyl-4-(1,1,3-trimethylhexyl)-6-(1,1-dimethylbutyl) phenol
2,4-bis(1,1,3,3-tetramethylbutyl)-6-(1,1-dimethylpropyl)phenol
2,6-bis(1,1-dimethylbutyl)-4-(1,1,3-trimethylhexyl)phenol
2.6(bis(1,1-dimethylbutyl)-4-(1-methylheptadecyl)phenol
2,6-bis(1,1-dimethylbutyl)-6-(1-methylheptyl)phenol
2,4-bis(1,1,3,3-tetramethylbutyl)-6-(1,1-dimethylbutyl)phenol
2,4-bis(1,1,3-trimethylhexyl)-6-(1,1-dimethylpropyl)phenol
2,4-bis(1-methylundecyl)-6-methylphenol
2,4,6-trinonylphenol
2,4-bis(1-methyltridecyl)-6-methylphenol
The phenolic antioxidants of the present invention are synthesized by well known methods of alkylation of phenol and monosubstituted phenols consisting of o, m and p isomers. The preferred process is to treat the phenol or monsubstituted phenol with the appropriate olefins in the presence of a Friedel Craft type catalyst at a temperature of between 0°C. and 150°C. Preferred catalysts are H2 SO4, the sulfonic acids and acid activated clays. Exact conditions such as catalyst quantity, temperature, molar ratios of olefin to phenol will depend upon the phenol and olefin being used, but are well known in the art. In case of dissimilar groups, such as tert.octyl and tert.butyl, mixtures of olefins may be used, but here it is preferred to react with the least active olefin first. Other alkylating agents such as alcohols and alkyl halides may be used; however, these agents are not preferred. Aluminum phenates may also be used as alkylation catalysts.
The present invention provides a way to reduce latex viscosities, compounded and uncompounded, without causing processing difficulties or adversely affecting the properties of the latex of the products treated with said latex or products fabricated therefrom. The viscosity depressants can be added to latices prior to foam formation, thereby decreasing the froth viscosity. This results in easier pouring of the foamed latex and/or improved spreading characteristics when forming carpet backing. The depressants can also be added to latices to improve pumping efficiency. Addition to latices to be compounded will permit the addition of higher amounts of inorganic fillers, e.g., where the latex is to be used to coat paper or to form a foamed product. The depressants also facilitate easier mixing of the fillers into the latices. Where a latex is being used to coat paper, the depressants can be used to reduce the viscosity of a compounded latex which otherwise would be so viscous that it would result in a non-uniform coating. The depressants can also be incorporated into latices whcih are to be used at lower temperatures. Where a fabric is being coated with a latex, and then being dried, it may be necessary due to the high viscosity of the latex, that the fabric be coated slowly to permit sufficient penetration of the latex into the fabric before the drying step. The addition of the viscosity supressant to the latex will result in a faster penetration rate and therefore permit a faster coating rate.
In foam manufacture, the latices used often possess a high viscosity. This is normally due to the need for high solids latex, for example, 60 percent solids and above and sometimes because of compounding the latex with high amounts, i.e., 50 to 100 parts by weight and above, of fillers. The high solids requirement is based on the fact that as low a water level as possible is desirable from a shrinkage and drying standpoint. Various problems can result because of the high viscosity. Included in these problems are low pumping rates, low spreading rates, and poor foaming rates. The viscosity depressants of the present invention, by addition to the latex, can result in reasonable viscosities without sacrificing the high solids contents and high levels of loading. On the other hand, where a highly loaded, high solids latex possesses a reasonable viscosity, but it is desirable to increase solids and/or the loading level without increasing viscosity, the present depressants can be added to the latex.
The high viscosity latices which benefit by the practice of the present invention are those latices both compounded and uncompounded which have a viscosity of at least 500 centipoises. Viscosity as referred to herein is conveniently measured according to ASTM D 1417-7 (1970 Annual Book of ASTM Standards, Vol. 28), the viscosity normally being measured with a Brookfield Viscometer. The depressants are particularly beneficial in latices having even higher viscosities such as those having a viscosity in the absence of these viscosity depressants of at least two or three thousand. The depressants are most beneficial in latices having a viscosity of at least 4000 centipoises.
The polymer latices that can benefit by the practice of the present invention include latices of substituted and unsubstituted, saturated and unsaturated, natural and synthetic polymers. The synthetic polymers are prepared by any of the well known free radical emulsion polymerizaton techniques. The oxidizable natural polymers include natural rubber in its various forms, e.g., pale crepe and smoked sheet, and balata and gutta percha. The oxidizable synthetic polymers, including rubbery synthetic polymers, are prepared from a single monomer (homopolymer) or a mixture of two or more copolymerizable monomers (copolymers) wherein the monomers are combined in a random distribution or block form. The monomers may be substituted or unsubstituted and may possess one or more double bonds, for example, diene monomers such as conjugated dienes, and polymerizable monoolefins, especially vinyl and vinylidene monomers. Examples of conjugated dienes are 1,3-butadiene, isoprene, chloroprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl 1,3-butadiene and piperylene. Examples of vinyl monomers are styrene, acrylonitrile, acrylic acid, ethylacrylate, butylacrylate, methyl vinyl ether, vinyl acetate and vinyl pyridine. Examples of vinylidene monomers are α-methylstyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and vinylidene chloride. Representative examples of the synthetic polymer latices used in the practice of this invention are latices of homopolymers of a conjugated 1,3-diene such as isoprene and butadiene, and copolymers of a conjugated 1,3-diene such as isoprene and butadiene with up to 50 percent by weight of at least one copolymerizable monomer, especially vinyl and vinylidene monomers, such as styrene, acrylonitrile or vinylidene chloride. The depressants are particularly beneficial in latices used in the manufacture of foam rubber both natural and synthetic. They are also quite beneficial in latices used to coat and sometimes impregnate paper products. The latices used in all of these applications are well known. The operations involved in preparing foamed products and in coating and impregnating paper are also quite well known in the art. Some of the latices used in forming foam rubber products are described in U.S. Pat. Nos. 3,523,996; 3,496,055; 3,493,523 and 2,649,391. Latices for coating paper are represented by those described in U.S. Pat. Nos. 3,047,427 and 3,399,080. The latices used in making foam rubber are normally either natural rubber latices or a synthetic rubber latex, at least 40 to 50 percent of the bound monomer units being the segmeric form of a conjugated 1,3-diene such as 1,3-butadiene. Typical latices used in coating paper include butadiene-styrene latices and polyacrylate latices.
The viscosity depressants are added to the latex in liquid form, normally in the form of an emulsion. If the depressant is a solid, it is dissolved in an appropriate organic solvent such as toluene before being emulsified. Conventional emulsifiers, cationic, anionic or non-ionic are used. The solvents used to dissolve the solid depressant should have limited compatibility with the polymer in the latex to which the depressant is added.
In addition to acting as a viscosity depressant, the compounds of the present invention offer at least a small degree of antioxidant effectiveness. Therefore, every one of the depressants of the present invention serves a dual purpose. Not only do they reduce the viscosity of the latex to which they are added, but in addition they protect the polymer at least to some degree against oxidative degradation. They also are relatively nondiscoloring. As a result of their dual functionality, the better antioxidants of the phenolic compounds described herein afford an economic and step saving advantage in that often one need not incorporate two additives, i.e., both a viscosity depressant and an antioxidant, but only one additive which serves both functions.
The amount of phenolic compound to be added to the latex will depend naturally upon the particular depressant which is added, the viscosity of the latex to which it is added and the desired viscosity. Levels of from 0.10 part to 5.0 parts by weight of depressant per 100 parts by weight of polymer in the polymer latex and higher can be used. Most of the viscosity depressant effect, however, can be obtained normally by using as little as 1.0 to 3.0 parts. A preferred range is 0.25 to 3.0 parts, most preferably from 0.50 to 3.0 parts.
The viscosity depressant effect of the subject compounds is not normally permanent. Although the viscosity drops quickly as the depressant is added, it tends to rise and return toward the original viscosity with time. It is not completely clear what factors affect this time period. However, it is believed that the duration of depressant activity may be associated with the emulsifier used to emulsify the depressant. It is theorized that possibly when the emulsifier used to emulsify the depressant is similar to the emulsifier used to prepare the polymer latex, the duration of viscosity activity is shortened. Therefore, when it is desirable to reduce viscosity for a particular operation, preferably the depressant is added shortly before the operation.
The following working examples illustrate the preparation of phenolic viscosity depressants within the practice of the present invention.
The phenolic compound, 2,4,6-tris-(1,1-dimethylbutyl) phenol is prepared in the following manner. Ninety-four grams of phenol and 20 grams of toluene sulfonic acid are heated together at a temperature of 120° C. and 90 grams of 2-methyl-1-pentene are added over a 30 minute period. The mixture is cooled to 30° C. and the remaining 180 grams of 2-methyl-1-pentene are added dropwise over a 2 hour period. The reaction mixture is stirred 30 minutes longer and then neutralized with 20 grams of sodium carbonate in an aqueous solution. After decanting the aqueous layer, the product is stripped to a bottom temperture of 150° C. under vacuum.
Ninety-four grams of phenol, 4 grams of sulfuric acid and 12 grams of activated clay are heated to 60° C. At that temperature 224 grams of diisobutylene are added over a 2 hour period. After stirring the combination for 2 hours, 56 grams of isobutylene are added. The product is neutralized with 10 grams of sodium carbonate in 90 milliliters of water. The water layer is decanted. The product is stripped to a bottom temperature of 174° C. and a column temperature of 150° C. at 20 millimeters of mercury in the presence of 2 grams of dry sodium carbonate.
2,4-bis(1,1,3-trimethylhexyl) phenol is prepared in the following manner. Ninety-four grams of phenol and 20 grams of toluene sulfonic acid are heated together to 85° C. 2,4-dimethyl-1-heptene is added in the amount of 304 grams dropwise over a 3 hour period. The mixture is stirred 2 hours and neutralized with 20 grams of sodium carbonate in aqueous solution. After decanting 5 grams of dry sodium carbonate are added and the product is distilled. The fraction boiling at a column temperature of from 165° C. to 170° C. at 1.1 millimeters of mercury is collected.
The following examples illustrate, but are not intended to limit, the practice of the present invention.
Pliolite* 5362, an SBR latex which can be used for foam rubber applications and having a solids content of approximately 68 percent, was compounded with a feldspar-type filler (125 parts by weight per 100 parts by weight of latex solids). Various phenolic compounds were emulsified using potassium oleate and added to the loaded latex. They were all added in the amount of 2.50 parts by weight of the phenolic compound per 100 parts by weight of the latex solids. The average viscosity of the latex containg the feldspar-type filler before the addition of the phenolic compounds was 13,470 centipoises using a Model HAT Brookfield Viscometer and a number 2 spindle at 5 revolutions per minute. The viscosity of the latex was measured shortly after the addition of the phenolic compounds.
Specifically a 20 percent aqueous solution of potassium oleate was added to the latex in an amount sufficient to provide 4 parts by weight of potassium oleate per 100 parts by weight of latex solids. The oleate aids in stabilizing the latex during the filler addition. The feldspar filler was then added in dry form under agitation to the latex. Viscosity measurements were made on the loaded latex, small amounts of water being added if necessary to facilitate easier measurement of the viscosity. Fifty percent aqueous emulsions of the phenolic compounds, with sodium oleate as the emulsifier, were added to the latex under agitation. Viscosity measurements were made shortly thereafter.
All of the Examples 4, 5 and 6 involve the use of phenolic viscosity depressants within the practice of the present invention. Example 4 involves the use of a trihexylated phenol. Example 5 involves a compound which is a mixture of butylated and octylated phenols, one of the main constituents being a phenolic compound containing a butyl group in an ortho position and octyl groups in the ortho and para positions. Example 6 involves the use of a phenolic compound having a single large alkyl substituent.
The results are tabulated in Table I. The Depressant Index was calculated by dividing the viscosity of the loaded latex after the addition of the viscosity depressant by the viscosity of the loaded latex prior to the addition of the viscosity depressant.
Table I
______________________________________
Depressant
Ex. Viscosity Depressant Index
______________________________________
4 2,4,6-tris-(1,1-dimethylbutyl)phenol
0.34
5 Similar to the product of Example 2
0.38
6 Poly(isobutyl)phenol.sup.(1)
0.33
(1) Poly(Isobutyl)Phenol-450 (PIBP-450)
having the structural formula
CH.sub.3 CH.sub.3
||
--(C--CH.sub.2).sub.n --C--CH.sub.3
||
CH.sub.3 CH.sub.3
______________________________________
Average Molecular Weight = ca.450 n(ave) = 5
Available from Rohm and Haas Company
The above data demonstrates the effectiveness of compounds used within the practice of the present invention in reducing the viscosity of a compounded latex. In each case the viscosity was reduced to about one-third of the original viscosity. Naturally water added as part of the emulsion has an effect on viscosity, but the phenolic compounds themselves were responsible for the major portion of the reduction. Tests would indicate that all three of the compounds offer some degree of protection against oxidation, although the depressants in Examples 4 and 5 would be superior in this respect to the compound of Examples 6.
The phenolic compound of Example 6 was butylated and used as a depressant. It's Depressant Index was 0.30.
Two phenolic antioxidants not within the scope of the present invention were tested along with the depressants described in Examples 4, 5 and 6. One antioxidant was a styrenated phenol. The other was a butylated, styrenated m-p, cresol. Neither reduced the latex viscosity. In fact, both antioxidants increased the viscosity of the latex.
The previous examples only illustrate the practice of the present invention. They do not limit it. Any of the viscosity depressants specifically recited or generically described herein, such as 2,4-bis(1,1,3-trimethylhexyl)phenol (Example 3), can be substituted in working examples 4, 5 or 6 for the viscosity depressants used. Such a substitution would result in a reduction in the latex viscosity. Also any of the latices described earlier herein, such as natural rubber latex or polybutadiene latex, could be substituted in whole or in part for the SBR latex used in Examples 4, 5 and 6. In each case the latex viscosity would be reduced. This is true for both compounded and uncompounded latices. In fact the viscosity of a 50/50 blend of natural rubber and SBR latices has been reduced by a combination of the phenolic compound of Example 1 and another viscosity depressant.
These viscosity depressants can also be used in combination with other antioxidants such as those described in U.S. Pat. No. 3,305,522.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
Claims (14)
1. A polymer latex wherein the polymer is selected from the group consisting of natural rubber, homopolymers of conjugated 1,3-diene monomer, and copolymers of conjugated 1,3-diene monomer with at least one copolymerizable monomer selected from the group consisting of vinyl monomers and vinylidene monomers, said copolymers containg up to 50 percent by weight of the copolymerizable monomer, said polymer latex having an original latex viscosity of at least 500 centipoises having incorporated therein 0.25 to 3.0 parts by weight of a liquid phenolic viscosity depressant per 100 parts by weight of polymer in the polymer latex said phenolic viscosity depresssant having the following structural formula ##SPC2##
wherein R, R1 and R2 are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 24 carbon atoms and wherein the sum of the carbon atoms in R, R1 and R2 is from 14 to 32 carbon atoms wherein the liquid depressant is in emulsion form.
2. The polymer latex according to claim 1 wherein R and R1 contain 4 to 8 carbon atoms, are in positions ortho to the hydroxyl group and are attached to the phenolic ring by a tertiary carbon atom and wherein R2 contains 6 to 24 carbon atoms and is in a position para to the hydroxyl group.
3. The polymer latex according to claim 2 wherein R2 contains 6 to 12 carbon atoms.
4. The polymer latex according to claim 1 wherein R2 is an alkyl radical containing 18 to 24 carbon atoms and is in a position para to the hydroxyl group.
5. The polymer latex according to claim 1 wherein R1 and R2 are alkyl radicals containing at least 9 carbon atoms each and wherein R1 and R2 are in positions ortho and part to the hydroxyl group.
6. The polymer latex according to claim 1 wherein the original latex viscosity is at least 4000 centipoises.
7. The polymer latex according to claim 1 wherein the latex is compounded latex containing a filler.
8. The polymer latex according to claim 7 wherein the filler is present in the amount of at least 20 parts of filler per 100 parts by weight of polymer in the latex.
9. The polymer latex according to claim 1 wherein the viscosity depressant is 2,4,6-tris-(1,1-dimethylbutyl) phenol.
10. The polymer latex according to claim 1 wherein the polymer latex is selected from the group consisting of polymer latex of copolymers of 1,3-butadiene and styrene and polymer latex of copolymers of 1,3-butadiene and acrylonitrile wherein said polymers contain up to 50 percent by weight of the styrene or acrylonitrile and natural rubber latex.
11. The polymer latex according to claim 1 wherein the conjugated 1,3-diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and piperylene, and the copolymerizable monomer is selected from the group consisting of styrene, acrylonitrile, acrylic acid, ethylacrylate, butylacrylate, methyl vinyl ether, vinyl acetate, vinyl pyridine, α-methylstyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and vinylidene chloride.
12. A process of reducing the viscosity of a polymer latex having a viscosity of at least 500 centipoises, wherein the polymer is selected from the group consisting of natural rubber, homopolymers of conjugated 1,3-diene monomer, and copolymers of conjugated 1,3-diene monomer with at least one copolymerizable monomer selected from the group consisting of vinyl monomers and vinylidene monomers, said copolymers containing up to 50 percent by weight of the copolymerizable monomer, comprising incorporating therein 0.25 to 3.0 parts by weight of a liquid viscosity depressant per 100 parts by weight of polymer in he polymer latex, said viscosity depressant having the following structural formula ##SPC3##
wherein R, R1 and R2 are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 24 carbon atoms and wherein the sum of the carbon atoms in R, R1 and R2 is from 14 to 32 carbon atoms, wherein the depressant is in the form of an emulsion.
13. The process according to claim 12 wherein the latex is selected from the group consisting of polymer latex of copolymers of 1,3-butadiene and styrene and polymer latex of copolymers of 1,3-butadiene and acrylonitrile wherein sad polymers contain up to 50 percent by weight of the styrene or acrylonitrile and natural rubber latex.
14. The process according to claim 13 wherein the conjugated 1,3-diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and piperylene, and the copolymerizable monomer is selected from the group consisting of styrene, acrylonitrile, acrylic acid, ethylacrylate, butylacrylate, methyl vinyl ether, vinyl acetate, vinyl pyridine, α-methylstyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and vinylidene chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/328,212 US3959207A (en) | 1971-01-18 | 1973-01-31 | Latex viscosity depressants |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10748771A | 1971-01-18 | 1971-01-18 | |
| US05/328,212 US3959207A (en) | 1971-01-18 | 1973-01-31 | Latex viscosity depressants |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10748771A Continuation | 1971-01-18 | 1971-01-18 |
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| Publication Number | Publication Date |
|---|---|
| US3959207A true US3959207A (en) | 1976-05-25 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/328,212 Expired - Lifetime US3959207A (en) | 1971-01-18 | 1973-01-31 | Latex viscosity depressants |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1980000971A1 (en) * | 1978-11-13 | 1980-05-15 | Gen Electric | Process for rendering aromatic polymers resistant to discoloration |
| US4273632A (en) * | 1976-04-22 | 1981-06-16 | Mobil Oil Corporation | Aminoplast-containing radiation curing coating compositions |
| EP0942037A1 (en) * | 1998-03-10 | 1999-09-15 | Basf Aktiengesellschaft | Polymer dispersions or solutions containing stabilisers and polymer preparations obtainable therefrom |
| JP2023513309A (en) * | 2020-02-14 | 2023-03-30 | シェブロン・オロナイト・カンパニー・エルエルシー | Alkyl-substituted hydroxyl aromatic compounds with highly structured alkyl branches |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3048563A (en) * | 1958-05-13 | 1962-08-07 | Bayer Ag | Composition comprising rubber and 2, 6-di-tertiary-butyl-3-methylphenol |
| US3477987A (en) * | 1963-11-13 | 1969-11-11 | Uniroyal Inc | Protection of olefinic polymers |
-
1973
- 1973-01-31 US US05/328,212 patent/US3959207A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3048563A (en) * | 1958-05-13 | 1962-08-07 | Bayer Ag | Composition comprising rubber and 2, 6-di-tertiary-butyl-3-methylphenol |
| US3477987A (en) * | 1963-11-13 | 1969-11-11 | Uniroyal Inc | Protection of olefinic polymers |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4273632A (en) * | 1976-04-22 | 1981-06-16 | Mobil Oil Corporation | Aminoplast-containing radiation curing coating compositions |
| WO1980000971A1 (en) * | 1978-11-13 | 1980-05-15 | Gen Electric | Process for rendering aromatic polymers resistant to discoloration |
| EP0942037A1 (en) * | 1998-03-10 | 1999-09-15 | Basf Aktiengesellschaft | Polymer dispersions or solutions containing stabilisers and polymer preparations obtainable therefrom |
| JPH11349686A (en) * | 1998-03-10 | 1999-12-21 | Basf Ag | Polymer dispersion or solution, its preparation and use thereof |
| US6214929B1 (en) | 1998-03-10 | 2001-04-10 | Basf Aktiengesellscaft | Stabilized polymer dispersions or polymer solutions, and prepared polymers obtainable therefrom |
| JP2023513309A (en) * | 2020-02-14 | 2023-03-30 | シェブロン・オロナイト・カンパニー・エルエルシー | Alkyl-substituted hydroxyl aromatic compounds with highly structured alkyl branches |
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